Journal Pre-proofs Fabrication and Characterization of Electrospun ZnO nanofibers; Antimicrobial assessment Sapna Thakur, Manpreet Kaur, Way Foong Lim, Madan Lal PII: DOI: Reference:
S0167-577X(19)31911-1 https://doi.org/10.1016/j.matlet.2019.127279 MLBLUE 127279
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Materials Letters
Received Date: Revised Date: Accepted Date:
19 July 2019 13 December 2019 27 December 2019
Please cite this article as: S. Thakur, M. Kaur, W.F. Lim, M. Lal, Fabrication and Characterization of Electrospun ZnO nanofibers; Antimicrobial assessment, Materials Letters (2019), doi: https://doi.org/10.1016/j.matlet. 2019.127279
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Fabrication and Characterization of Electrospun ZnO nanofibers; Antimicrobial assessment. Sapna Thakur1, Manpreet Kaur2, Way Foong Lim3 and Madan Lal 2,4* 1Department
of Biotechnology, Akal College of Agriculture, Eternal University, Sirmour (HP) 173101, India
2Department
of Physics, Akal College of Basic Sciences, Eternal University, Sirmour (HP) 173101, India
3Institute
of Nano Optoelectronics Research and Technology (INOR), Universiti Sains Malaysia, 11800 Penang, Malaysia
4School
of Physics and Materials Science, Shoolini University (HP) 173229, India.
ABSTRACT: Antimicrobial activity of ZnO nanomaterials has received global interest due to high surface to volume ratio. In the present study, ultra‐thin ZnO nanofibers in poly vinyl alcohol (PVA) has been electrospun. Calcination of mentioned precursor fibers was done at 400 and 500°C for 3hrs, respectively. Rietveld refinement of XRD pattern confirms the hexagonal wurtzite structure (with space group = P63mc) of ZnO nanofibers. SEM images reveal that the ZnO nanofibers have an average diameter of 315-292 nm. The earliest findings suggest that electrospun ZnO nanofibers are effective at exterminating Escherichia coli and Staphylococcus aureus cells by the destruction of the cell wall and affecting the genetic material of the bacterial cells.
Keywords: X-ray technique, Biomaterials, Electrospun, Nanofibers, Antimicrobial. *Corresponding
Author E-mail address:
[email protected] (Madan Lal).
1. Introduction In the past few decades, nano-structured materials reflect diverse morphological groups like nanofibers, nanowires, nano rings, nanobelts, and nano cages, etc. Nano-structured materials possess pronounced scientific interest due to unique electrical, optical, microbial behavior and high surface area, and surface energy, as well as they comprise a metal cation and oxide anion [1-3]. ZnO is a multifunctional nano material which retains the band gap of 3.37 eV and exciton binding energy of 60 meV; with such property, it becomes anticipated material for an extensive range of applications like food preservation, manufacturing stability, and increasing the shelf life of products.[4] ZnO nano materials have been synthesized by using a different chemical and physical methods such as hydrothermal [5], chemical vapor deposition (CVD) [6], sol-gel [7] and electrospinning [8], green synthesis using various leaf extracts [9]. Fascinatingly, several studies conveyed that ZnO nanoparticles are non-toxic to human cells. In food packing and cosmetic industries, the ZnO nano structured materials have drawn much consideration due to its antimicrobial activity [10]. ZnO is well known to the community, science 3,000 years ago in the form of calamine lotions in prehistoric Ayurvedic manuscripts [11]. Metal nano-structured materials are ecofriendly, cost effective having good photo-oxidizing and photo-catalysis impacts on biotic species [8, 12]. Antimicrobial activity of any metal nano-structured materials is influenced by oxidative stress in microbial cells due to exposer to the surface of nano-materials which ultimately responsible for the microbial cells lysis [13, 14]. ZnO micron/nano-particles were studied for sustained antibacterial activity against Listeria monocytogenes for food packaging applications as well as possess high antimicrobial/photocatalytic activity at the low-intensity UV-LED device with good reusability [15, 16]. Electrospinning has been accepted as an unpretentious and effective technology to develop nanofibers using polymer solution in the electric field [17, 18]. ZnO nanofibers were recently successfully electrospun by using polymer solutions like polyvinyl
alcohol (PVA) [19], poly(methyl methacrylate) (PMMA) [20], or polyamide [18, 21]. Numerous studies were done on the development of ZnO nanofibers using polymer by electrospinning [22, 23]. In the present study, we are reporting the synthesis of ZnO nanofibers and their characterized via standard analytical tools: X-ray diffraction (XRD), and scanning electron microscopic (SEM). We also studied for its antibacterial activity against different pathogenic bacteria’s. 2. Materials and methods Zinc acetate (Zn(CH3COO)2.2H2O), poly vinyl alcohol (PVA), potassium hydroxide (KOH) was purchased from HiMedia (India) and used as raw materials for the synthesis of ZnO nanofibers. PVA solution was prepared by dissolving 1gm of PVA in distilled water and separately 5gm of Zinc acetate was dissolved in distilled water containing KOH. Mixing with mechanical stirring was performed for 3-4 h for complete solubility of both the solution at 70 °C. This homogeneous and transparent solution was then added into 10 ml plastic syringe. The final solution was electrospun under 15-20 kV electric field with a flow rate of 0.20 ml/h. The distance between the needle tip and metal collector was 12 cm. The electrospinning process was conducted on Al sheet substrates in a closed box maintained at a relative humidity about 30% and cabin temperature of 30 °C. The obtained fiber-mesh was annealed to obtain ZnO nanofibers at 400 (abbreviated as Zn400) and 500 °C (abbreviated as Zn500) for 3 hrs at constant heat flow rates (i.e. 1 oC/min) caused the elimination of water molecules from the zinc acetate and resulted in the formation of Zinc oxide (ZnO) as given in Eqn (1 and 2). Zn (CH3COO)2. H2O → Zn (CH3COO)2 + 2 H2O ↑ Zn (CH3COO)2 + 2K-OH → ZnO + 2KCH3COO + H2O
(1) (at calcination)
(2)
The surface morphologies of samples were analysed using a scanning electron microscope (SEM, JEOL 7600F). The structures were studied by X-ray diffraction (XRD, Bruker D8 Discover GADDS X-ray diffractometer) with Cu Kα radiation (λ = 0.154 nm). The scanning speed was 0.5 s/step and step size is 0.2°. 3. Results and discussion 3.1 Morphologies and structures study Fig. 1(a-b) show Rietveld refined XRD pattern of ZnO nanofibers at room temperature. However, the XRD spectrum of ZnO nanofibers exhibits well-defined diffraction peaks at 2θ of 31.7º, 34.4º, 36.3º, 47.5º and 56.6º corresponding to (100), (002), (101), (102), (110) planes matched with JCPDS file 751526. Rietveld refinement also confirms that both samples have a hexagonal wurtzite structure with space group (C6V = P63mc). The sharp and clear peaks confirm that ZnO nanofibers have pure crystalline phase. The various Rietveld refined parameters are listed in Table 1. Fig. 1 (c) shows the comparison of peak width along 101 planes. The average crystallite size was calculated from broadening of all XRD peaks by employing Scherrer equation [24] was found about 40.67 and 15.42 nm with annealing temperature 400 and 500, respectively. λ
D = 0.9 β cosθ
(1)
Fig. 2 shows the diameter of ZnO nanofibers decreased significantly with the increase in annealing temperature. The average diameter of ZnO nanofibers was around 800 nm without annealing (as shown in Fig. 2(a and a’)). However, the average diameter of ZnO nanofibers was found to be 315 and 292 nm (from Fig. 2(b and b’) & (c and c’)) with an annealing temperature of 400 and 500 ˚C respectively. The decomposition of PVA is the major cause for the shrinkage of the nanofibers during the annealing process. 3.2 Antimicrobial study
Antibacterial studies have demonstrated that ZnO nanofibers synthesized through electrospinning technique shows a significant growth inhibition against Gram negative bacteria Escherichia coli (MTCC-443) and Gram positive bacteria Staphylococcus aureus (MTCC-737). Toxicological studies of synthesized ZnO nanofibers on Escherichia coli and Staphylococcus aureus were accomplished by well diffusion method and zone inhibition studies. The effect of growth inhibition and antibacterial activity of ZnO nanofibers materials on Escherichia coli (MTCC-443) and Staphylococcus aureus (MTCC-737) is given in (Fig. 3. a-b). In the vitro antibacterial activity of nanofibers material against Staphylococcus aureus and Escherichia coli also shown in Table 2. The nanofibers of Zn400 and Zn500 were found effective against both the strains 11 mm and 10 mm against Staphylococcus aureus (MTCC-737) only and was observed 10 mm and 5 mm against Escherichia coli (MTCC-443) respectively. The earliest findings suggest that ZnO nanofibers materials synthesized are effective at exterminating Escherichia coli and Staphylococcus aureus cells by the destruction of the cell wall and affecting the genetic material of the bacterial cells [25-27]. 4.
Conclusions ZnO nanofibers has been synthesized successfully by using the electrospun method.
Rietveld refined of X-ray diffraction confirmed that nanofibers has a hexagonal wurtzite structure with the average crystalline size of 40.67 and 15.42 nm for ZnO nanofibers. SEM shows that ZnO nanofibers have diameter 315, and 292 nm. The findings suggest that electrospun ZnO nanofibers are effective at exterminating Escherichia coli and Staphylococcus aureus cells by the destruction of the cell wall and affecting the genetic material of the bacterial cells. It also reflects that different particle size has different activity with Staphylococcus aureus and Escherichia coli bacteria. The lowest particle size has a maximum activity. Acknowledgement
Authors are grateful to the Department of Science and Technology (DST), Govt. of India, for financial support under the research project SR/WOS-A/LS-296/2017. References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23]
E. Ghafari, Y. Feng, Y. Liu, I. Ferguson, N. Lu, Composites Part B: Engineering 116 (2017) 40-45. N. Korber, A. Fleischmann, Journal of the Chemical Society, Dalton Transactions (4) (2001) 383-385. S.P. Prabhavathi, J. Punitha, P.S. Rajam, R. Ranjith, G. Suresh, N. Mala, D. Maruthamuthu, J Chem Pharm Res 6 (2014) 1472-1478. K. Gold, B. Slay, M. Knackstedt, A.K. Gaharwar, Advanced Therapeutics 1(3) (2018) 1700033. Y. Sun, N.G. Ndifor-Angwafor, D.J. Riley, M.N. Ashfold, Chemical Physics Letters 431(4) (2006) 352-357. B. Xiang, P. Wang, X. Zhang, S.A. Dayeh, D.P. Aplin, C. Soci, D. Yu, D. Wang, Nano letters 7(2) (2007) 323-328. Y.-S. Kim, W.-P. Tai, S.-J. Shu, Thin Solid Films 491(1) (2005) 153-160. P. Samanta, S. Bagchi, S. Mishra, Materials Today: Proceedings 2(9) (2015) 44994502. D. Suresh, P. Nethravathi, H. Rajanaika, H. Nagabhushana, S. Sharma, Materials Science in Semiconductor Processing 31 (2015) 446-454. H.S. Lalithamba, M. Raghavendra, K. Uma, K.V. Yatish, D. Mousumi, G. Nagendra, Acta Chimica Slovenica (2018). A.S. Prasad, Nutrition (Burbank, Los Angeles County, Calif.) 11(1 Suppl) (1995) 9399. S. Thakur, R. Kumar, J Mol Genet Med 12(324) (2018) 1747-0862.1000324. R. Hong, J. Qian, J. Cao, Powder Technology 163(3) (2006) 160-168. S.B. Rana, R. Singh, S. Arya, Journal of Materials Science: Materials in Electronics 28(3) (2017) 2660-2672. J.L. Castro-Mayorga, M.J. Fabra, A.M. Pourrahimi, R.T. Olsson, J. Lagaron, T Food, and Bioproducts Processing 101 (2017) 32-44. J.H. Kim, M.K. Joshi, J. Lee, C.H. Park, C.S. Kim, Journal of colloid and interface science 513 (2018) 566-574. Y. Zhang, J. Venugopal, Z.-M. Huang, C. Lim, S. Ramakrishna, Biomacromolecules 6(5) (2005) 2583-2589. E.F. de Melo, K.G. Alves, S.A. Junior, C.P. de Melo, Journal of Materials Science 48(10) (2013) 3652-3658. H. Hallaji, A.R. Keshtkar, M.A. Moosavian, Journal of the Taiwan Institute of Chemical Engineers 46 (2015) 109-118. Y.-S. Chen, G.-W. Hsieh, S.-P. Chen, P.-Y. Tseng, C.-W. Wang, ACS applied materials & interfaces 7(1) (2014) 45-50. R.S. Andre, A. Pavinatto, L.A. Mercante, E.C. Paris, L.H. Mattoso, D.S. Correa, RSC Advances 5(90) (2015) 73875-73881. J.-A. Park, J. Moon, S.-J. Lee, S.-C. Lim, T. Zyung, Current Applied Physics 9(3) (2009) S210-S212. H. Yu, H. Fan, X. Wang, J. Wang, Optik-International Journal for Light and Electron Optics 125(10) (2014) 2361-2364.
[24] [25] [26] [27]
R. Yogamalar, R. Srinivasan, A. Vinu, K. Ariga, A.C. Bose, Solid State Communications 149(43-44) (2009) 1919-1923. B. Ahmed, B. Solanki, A. Zaidi, M. S. Khan, J. Musarrat. Toxicology research, 8(2) (2019) 246-261. S. Esparza-González, S. Sánchez-Valdés, S. Ramírez-Barrón, M. Loera-Arias, J. Bernal, H. I. Melendez-Ortiz, R. Betancourt-Galindo, Toxicology in Vitro, 37, (2016) 134-141. A. Sirelkhatim, S. Mahmud, A. Seeni, N. H. M. Kaus, L. C. Ann, S. K. M. Bakhori, H. Hasan, D. Mohamad, Nano-Micro Letters, 7(3) (2015) 219-242.
Highlights
ZnO nanofibers were synthesized by electrospinning method.
ZnO nanofibers have hexagonal wurtzite structure with space group (C6V=P63mc).
SEM images shows ZnO nanofibers have average diameter 315, and 292 nm, respectively.
ZnO nanofibers have antimicrobial activity against S. aureus & E. coli bacteria.